Journal of Physical Chemistry A, Vol.104, No.48, 11282-11289, 2000
Model for spectral artifacts in two-dimensional four-wave mixing spectra from absorption and refractive index dispersion at infrared resonances
Doubly vibrationally enhanced four-wave mixing (DOVE-FWM) is a new technique that is capable of providing two-dimensional spectra. These methods often require scanning lasers over infrared absorption features where the index of refraction dispersion and the sample absorption distort the 2D spectra. In order to test a quantitative model for treating these artifacts, we have chosen a simple model system with an isolated absorption feature and we have compared the line shapes of a resonant Raman feature for a series of different concentrations and experimental scanning strategies. We have identified the 2D spectral signatures that accompany the dispersion and absorption effects and we have shown that they are qualitatively similar to the effects introduced by singly vibrationally enhanced (SIVE) four-wave mixing. We find that the spectral changes are substantial and must be treated correctly if one is to obtain an accurate treatment of multiresonant data.